1. Field of the Invention
The present invention relates to the production of the cis-dihydrodiol derivative of diphenylacetylenes and the dehydration thereof to form the corresponding meta-substituted phenol derivative. Use of alkali, preferably at elevated temperature, optimizes production of 3-hydroxydiphenylacetylene over 2-hydroxydiphenylacetylene.
2. Description of the Related Art
Compounds of the general formula ##STR3## have been chemically dehydrated to phenols by acidification. In general, the 2-hydroxy isomer predominates, or is the exclusive product of the reaction. More recently, U.S. patent application Ser. No. 07/623,581, filed Dec. 7, 1990, discloses the use of a base to optimize production of the 3-hydroxy isomer of certain such compounds.
U.S. Pat. No. 4,508,822 discloses the preparation of compounds of the general formula ##STR4## wherein X and Y may be the same or different, and represent hydrogen, halogen, ceryl, or cyano groups except that X and Y cannot both be hydrogen, using strains of Pseudornonas putida.
U.S. Pat. No. 4,532,209 discloses the production of p-cresol by the acidification of an aqueous solution of 4-methylcyclohexa-3,5-diene-1,2-diol- 1-carboxylic acid.
The formation of (+)-cis-2,3-dihydroxy-1-methylcyclohexa-4,6-diene from toluene by Pseudomonas putia, is disclosed by D. T. Gibson et al., Biochemistry, pp. 1626-1630, Vol. 9, (1970) along with the acid catalyzed dehydration of (+)-cis-2,3-dihydroxy-1-methylcyclohexa -4,6-diene.
U.K. Patent No. 2,203,150 B discloses preparing fluorophenols by dehydrating 1,2-dihydroxy-3-fluorocyclohexa-3,5-diene in the presence of base and subsequently recovering 2 and/or 3-fluorophenol. The use of base does not make the reaction overly selective for 3-fluorophenol.
Initial Reactions in the Oxidation of Ethylbenzene by Pseudomonas putida, by D. T. Gibson et al., Biochemistry, pp. 1520-1527, Vol. 12, No. 8, (1973) discloses the oxidation of ethyl benzene to (+)-cis-3-ethyl-3,5-cyclohexadiene-1,2-diol and (+)-cis-3-(1'-hydroxyethyl)-3,5-cyclohexadiene-1,2-diol by Pseudomonas putida as well as the oxidation of acetophenone to cis-3-(1'-oxoethyl)-3,5-cyclohexadiene-1,2-diol. The reference also discloses the acid catalyzed dehydration of (+)-cis-3-ethyl-3,5-cyclohexadiene-1,2-diol.
Biodegradations Yield Novel Intermediates For Chemical Synthesis, D. W. Ribbons et al., Biotechnology and Biodegradations, pp. 2 13-245, London discloses the use of routants of P. putida to form compounds of the formula ##STR5## where R.sup.1 =R.sup.2 =H; R.sup.1 =Cl, R.sup.2 =H; R.sup.1 =F, R.sup.2 =H; R.sup.1 =CH.sub.3, R.sup.2 =H; R.sup.1 =Ph, R.sup.2 =H; R.sup.1 =CF.sub.3, R.sup.2 =H; R.sup.1 =C.sub.2 H.sub.5, R.sup.2 =H; R.sup.1 =HC=CH.sub.2, R.sup.2 =H; R.sup.1 =C=CH,R.sup.2 =H; R.sup.1 =CH.sup.3,R.sup.2 =F; R.sup.1 =CH.sup.3, R.sup.2 =Cl; R.sup.1 =CH.sub.3, R.sup.2 =Br.
U.S. Pat. No. 4,081,468 discloses acetylenic compounds of the formula R.sup.3- C=C--R.sup.4 where R.sup.3 is selected from the group consisting of hydroxy, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, hydroxy substituted cycloalkyl, hydroxy substituted phenyl, hydroxy substituted phenalkyl, amino substituted alkyl and alkyl substituted by the group --O--C(O)-alkyl, and R.sup.4 is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, phenalkyl, hydroxyalkyl, hydroxyalkenyl, hydroxy cycloalkyl, hydroxyalkenyl, hydroxy cycloalkyl, hydroxy substituted phenyl, hydroxy substituted phenalkyl, amino alkyl and alkyl substituted by the group --O--C(O)-alkyl.
U.S. Pat. No. 4,153,509 discloses preparing compounds of the formula ##STR6## wherein, m and o are individually 1 or 0 with the proviso that both m and o may not be 0, n is 0, 1 or 2; and x is phenyl, divalent oxygen, sulfur, sulfinyl, sulfonyl, carbonyl, am/no or alkylamino or x is a divalent alkylene, alkenylene or alkynylene chain which may optionally include one or more divalent oxygen, sulfur, sulfinyl, sulfonyl, carbonyl, amino or alkylamino moieties in any combination by enzymatically biotransforming the corresponding biphenyl compound with a microorganism.
U.S. Pat. No. 4,772,755 discloses compounds of the formula ##STR7## wherein x is hydroxy, alkoxy or alkanoyloxy, Ar.sup.1 is an organic group such as phenyl which may be independently substituted by one or more of alkyl, alkoxy, alkylthio, dialkylamino, halogen etc. and R is an unsubstituted or substituted alkyl group.
EP 400,779 A1 discloses production of meta-hydroxyphenyacetylenes from phenyl-substituted ketal or acetal precursors.